CN110214155B - Fluorinated block copolymers derived from nitrile cure site monomers - Google Patents

Fluorinated block copolymers derived from nitrile cure site monomers Download PDF

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CN110214155B
CN110214155B CN201880007484.9A CN201880007484A CN110214155B CN 110214155 B CN110214155 B CN 110214155B CN 201880007484 A CN201880007484 A CN 201880007484A CN 110214155 B CN110214155 B CN 110214155B
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block
fluorinated
curable composition
vdf
tfe
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CN110214155A (en
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迈克尔·H·米切尔
丹尼斯·杜谢恩
福士达夫
拉里·A·拉斯特
彼得·J·斯科特
卡尔·D·韦兰德特
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/28—Hexyfluoropropene
    • C08F214/282—Hexyfluoropropene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1458—Monomers containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Abstract

The present invention provides a curable composition comprising a fluorinated block copolymer having (a) at least one a block, wherein the a block is a semi-crystalline segment comprising repeating divalent monomer units derived from at least one fluorinated monomer; and (B) at least one B block, wherein the B block is a segment comprising repeating divalent monomer units comprising at least one fluorinated monomer and a nitrile-containing cure site monomer.

Description

Fluorinated block copolymers derived from nitrile cure site monomers
Technical Field
Fluorinated block copolymers that can be processed as elastomers are described.
Disclosure of Invention
There is an increasing demand for higher temperature elastomers that function adequately at temperatures of, for example, 200 ℃ to 330 ℃. Perfluoroelastomers (fully fluorinated molecules) have traditionally been used under these extreme temperature conditions due to the higher bond energy of the C-F bond. For certain applications and markets, however, the cost of perfluoroelastomers may make them undesirable or prohibitive.
Partially fluorinated elastomers are generally less expensive than perfluorinated elastomers and because they contain some fluorine they can perform adequately under some of the same extreme conditions as perfluorinated elastomers, such as chemical resistance, etc. However, partially fluorinated elastomers have traditionally had poor tensile properties at high temperatures, and therefore partially fluorinated elastomers having high tensile strength at high temperatures are desired.
Accordingly, it is desirable to identify fluorinated polymeric materials having improved properties such as high modulus. In some embodiments, it is also desirable to process the material as an elastomer, for example, by a two-roll mill or internal mixer.
In one aspect, a curable composition is provided comprising a fluorinated block copolymer having
(a) At least one A block, wherein the A block is a semi-crystalline segment comprising repeating divalent monomer units derived from at least one fluorinated monomer;
(b) at least one B block, wherein the B block is a segment comprising repeating divalent monomer units derived from at least one fluorinated monomer and a nitrile-containing cure site monomer.
The above summary is not intended to describe each embodiment. The details of one or more embodiments of the invention are set forth in the detailed description below. Other features, objects, and advantages will be apparent from the description and from the claims.
Detailed Description
As used herein, the term
"a," "an," and "the" are used interchangeably and refer to one or more; and
"and/or" is used to indicate that one or both of the recited conditions may occur, for example, A and/or B includes (A and B) and (A or B);
"backbone" refers to the predominantly continuous chain of the polymer;
"copolymer" means a polymeric material comprising at least two different comonomers (i.e., monomers that do not have the same chemical structure) and includes terpolymers (three different monomers), tetrapolymers (four different monomers), and the like;
"crosslinking" refers to the use of chemical bonds or groups to join two preformed polymer chains;
"cure site" refers to each functional group that can participate in crosslinking;
"glass transition temperature" or "Tg"refers to the temperature at which a polymeric material transitions from a glassy state to a rubbery state. Glassy states are typically associated with materials such as brittle, hard, rigid, or combinations thereof. In contrast, rubbery behavior is generally associated with materials such as flexibility and elasticity.
"interpolymerized" refers to monomers polymerized together to form a polymer backbone;
"grindable" is the ability of a material to be processed on rubber mills and internal mixers;
"monomer" is a molecule that can be polymerized and then form the basic structural moiety of a polymer;
"perfluorinated" means a group or compound derived from a hydrocarbon in which all hydrogen atoms have been replaced by fluorine atoms. However, the perfluorinated compounds may also contain other atoms than fluorine atoms and carbon atoms, such as chlorine atoms, bromine atoms, and iodine atoms. And is
"Polymer" refers to a macrostructure comprising interpolymerized units of monomers.
Also herein, the recitation of ranges by endpoints includes all numbers subsumed within that range (e.g. 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).
Also, herein, the expression "at least one" includes one and all numbers greater than one (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).
Thermoplastic elastomers are a class of materials that are copolymers or blends of polymers having both thermoplastic and elastomeric properties. Generally, the plastic component provides additional tensile strength, while the elastomeric component provides elasticity and compression set resistance to the material. Thermoplastic elastomers with a high plasticity component are traditionally processed similarly to plastics using, for example, extruders, injection molding equipment, and the like. Elastomeric materials, on the other hand, are typically processed using a two-roll mill or internal mixer. Mill blending is one method used by rubber manufacturers to mix polymer gums with the necessary curatives and/or additives. In order to grind the blend, the curable composition must have sufficient modulus. In other words, it is not so soft that it sticks to the mill, and not so hard that it cannot be attached to the mill.
The present disclosure relates to polymers having high modulus, which may be advantageous in some applications, such as gaskets and packer. In one embodiment, the block copolymers of the present disclosure can be processed in a similar manner as elastomers.
The present disclosure relates to fluorinated block copolymers. A "block copolymer" is a polymer in which chemically distinct blocks or sequences are covalently bonded to each other. The fluorinated block copolymers of the present disclosure comprise at least two different polymer blocks; these two blocks are referred to as the a block and the B block. The A and B blocks have different chemical compositions and/or different glass transition temperatures.
The a blocks of the present disclosure are semi-crystalline segments. If studied under Differential Scanning Calorimetry (DSC), the blocks will have at least one temperature greater than 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃ or even 150 ℃; and a melting point temperature (T) of at most 200 ℃, 250 ℃, 275 ℃, 300 ℃ or even 325 ℃m) And a measurable enthalpy, for example, greater than 0J/g (joules/gram) or even greater than 0.01J/g. Enthalpy is determined by the area under the curve of the melt transition measured using DSC for the tests disclosed herein and is expressed as joules/gram (J/g).
In one embodiment, the a block of the present disclosure is derived from at least one fluorinated monomer, wherein the monomer is defined as a molecule that can undergo polymerization.
(1) In one embodiment, the a blocks are derived from Tetrafluoroethylene (TFE); derived from TFE alone or TFE and a small amount (e.g., at least 0.1, 0.3, or even 0.5, and up to 0.8, 1,2, or even 3 weight percent) of other comonomers such as Hexafluoropropylene (HFP), vinylidene fluoride (VDF), Chlorotrifluoroethylene (CTFE), hexafluoroisobutylene, or perfluoroalkylethylene.
(2) In one embodimentThe a block is derived from TFE and fluorinated vinyl ethers such as perfluorovinyl ether and perfluoroallyl ether. Generally, these fluorinated ethers are used in an amount of at least 0.5, 1, or even 2 weight percent and at most 3,5, 8, or even 10 weight percent. Examples of perfluorovinyl ethers that can be used in the present disclosure include those corresponding to the formula: CF (compact flash)2＝CF-O-RfWherein R isfDenotes perfluorinated aliphatic groups which may not include an oxygen atom, include one or more oxygen atoms, and up to 12, 10, 8,6 or even 4 carbon atoms. Exemplary perfluorinated vinyl ethers correspond to the formula: CF (compact flash)2＝CFO(Ra fO)n(Rb fO)mRc fWherein R isa fAnd Rb fAre different linear or branched perfluoroalkylene groups having 1 to 6 carbon atoms, in particular having 2 to 6 carbon atoms, m and n are independently 0 to 10, and Rc fIs a perfluoroalkyl group having 1 to 6 carbon atoms. Specific examples of perfluorinated vinyl ethers include perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE), perfluoro (n-propyl vinyl) ether (PPVE-1), perfluoro-2-propoxypropyl vinyl ether (PPVE-2), perfluoro-3-methoxy-n-propyl vinyl ether, perfluoro-2-methoxy-ethyl vinyl ether, CF2＝CFOCF2OCF3、CF2＝CFOCF2OCF2CF3And CF3-(CF2)2-O-CF(CF3)-CF2-O-CF(CF3)-CF2-O-CF＝CF2. Examples of perfluoroallyl ethers that may be used in the present disclosure include those corresponding to the formula: CF (compact flash)2＝CF(CF2)-O-RfWherein R isfDenotes perfluorinated aliphatic groups which may contain no oxygen atoms, one or more oxygen atoms and up to 4,6, 8 or even 10 carbon atoms. Specific examples of perfluorinated allyl ethers include: CF (compact flash)2＝CF-CF2-O-(CF2)nF, wherein n is an integer from 1 to 5; and CF2＝CF-CF2-O-(CF2)x-O-(CF2)y-F, wherein x is an integer from 2 to 5 and y is an integer from 1 to 5. Specific examples of perfluorinated allyl ethers include perfluoro (methallyl) ether (CF)2＝CF-CF2-O-CF3) Perfluoro (ethyl allyl) ether, perfluoro (n-propyl allyl) ether, perfluoro-2-propoxypropyl allyl ether, perfluoro-3-methoxy-n-propyl allyl ether, perfluoro-2-methoxyethyl allyl ether, perfluoromethoxymethyl allyl ether, and CF3-(CF2)2-O-CF(CF3)-CF2-O-CF(CF3)-CF2-O-CF2CF＝CF2And combinations thereof.
(3) In one embodiment, the a blocks are derived from TFE and perfluoroolefin. Exemplary perfluoroolefins, such as Hexafluoropropylene (HFP), contain 2 to 8 carbon atoms. Generally, these perfluoroolefins are used in an amount of at least 2,3, or even 4 weight percent and at most 5, 10, 15, or even 20 weight percent. Other comonomers may be added in small amounts (e.g., less than 0.5, 1,2, 3, or even 5 wt%). Such comonomers may include, for example, fluorinated vinyl ethers as described above.
(4) In one embodiment, the a blocks are derived from TFE or CTFE (e.g., at least 40 wt% or even 45 wt%, and up to 50 wt%, 55 wt%, or even 60 wt%) and a non-fluorinated olefin (e.g., at least 40 wt% or even 45 wt%, and up to 50 wt%, 55 wt%, or even 60 wt%). Such non-fluorinated olefins contain 2 to 8 carbon atoms and include, for example, ethylene, propylene, and isobutylene. Other comonomers may be added in small amounts (e.g., at least 0.1 wt%, 0.5 wt%, or even 1 wt% and up to 3 wt%, 5 wt%, 7 wt%, or even 10 wt%). Such comonomers may include, for example, (per) fluoroolefins such as VDF or HFP; or a fluorinated vinyl ether as described above.
(5) In one embodiment, the a block is derived from VDF; derived from VDF alone or VDF and small amounts (e.g. at least 0.1 wt%, 0.3 wt% or even 0.5 wt% and up to 1 wt%, 2 wt%, 5 wt% or even 10 wt%) of other fluorinated comonomers such as (per) fluorinated olefins like HFP, TFE and trifluoroethylene.
(6) In one embodiment, the a block is derived from TFE, HFP, and VDF. In one embodiment, the a block comprises (a)30 to 85 wt.% TFE, 5 to 40 wt.% HFP, and 5 to 55 wt.% VDF; (b)30-75 wt% TFE, 5-35 wt% HFP, and 5-50 wt% VDF; (c)40-70 wt% TFE, 10-30 wt% HFP and 10-45 wt% VDF; or even (d)45-70 wt.% TFE, 10-30 wt.% HFP and 10-45 wt.% VDF; other comonomers may be added in small amounts (e.g., at least 0.1 wt% or even 0.5 wt% and up to 1 wt%, 3 wt%, 5 wt%, 7 wt%, or even 10 wt%). Such comonomers include perfluorovinyl ether and perfluoroallyl ether monomers as described above.
(7) In one embodiment, the A block is derived from TFE, HFP, VDF, and diolefin monomers (exemplary diolefin monomers are described below). In one embodiment, the A blocks comprise (a)30 to 85 weight percent TFE, 5 to 40 weight percent HFP, 5 to 55 weight percent VDF, and 0.01 to 1 weight percent diolefin monomer; (b)30-75 wt% TFE, 5-35 wt% HFP, 5-50 wt% VDF, and 0.01-1 wt% diolefin monomer; or even (c)40-70 wt.% TFE, 10-30 wt.% HFP, 10-45 wt.% VDF, and 0.01-1 wt.% diolefin monomer. Other comonomers may be added in small amounts (e.g., at least 0.1 wt% or even 0.5 wt% and up to 1 wt%, 3 wt%, 5 wt%, 7 wt%, or even 10 wt%). Such comonomers include perfluorovinyl ether and perfluoroallyl ether monomers as described above.
In one embodiment, the olefin monomer has the formula:
Figure BDA0002134695010000061
wherein R is1、R2、R3、R4、R5And R6Independently an H, C1-C5 alkyl group or a C1-C5 fluorinated alkyl group; and Z is linear or branched, optionally containing oxygen atoms andoptionally fluorinated alkylidene or cycloalkylidene groups. In one embodiment, R1、R2、R3And R4Independently of one another is F, CF3、C2F5、C3F7、C4F9、H、CH3、C2H5、C3H7Or C4H9. In one embodiment, Z comprises at least 1,2, 3, 4 or even 5 carbon atoms and up to 8, 10, 12, 16 or even 18 carbon atoms. In one embodiment, Z is-O-Rf1-O-；-CF2-O-Rf1-O-CF2-; or CF2-O-Rf1-O-, wherein Rf1Represents a residue selected from: linear or branched perfluorinated alkanediyl, perfluorinated oxaalkanediyl or perfluorinated polyoxoxaalkanediyl residues, or according to Rf2The residue of (1). In one embodiment, Rf1Comprises at least 1,2, 3, 4 or even 5 carbon atoms; and up to 8, 10, 12 or even 14 carbon atoms. Rf2Is a non-fluorinated, fluorinated or perfluorinated aromatic subunit. The arylene group can be unsubstituted or substituted with: one or more halogen atoms other than F, a perfluorinated alkyl residue, a perfluorinated alkoxy residue, a perfluorinated oxaalkyl residue, a perfluorinated polyoxaalkyl residue, a fluorinated, perfluorinated, or non-fluorinated phenyl or phenoxy moiety, or combinations thereof, wherein the phenyl or phenoxy residue may be unsubstituted or substituted with: one or more perfluorinated alkyl, alkoxy, oxaalkyl or polyoxaalkyl residues, or one or more halogen atoms other than F, or combinations thereof. In one embodiment, Rf2Comprises at least 1,2, 3, 4 or even 5 carbon atoms; and up to 10, 12 or even 14 carbon atoms.
Exemplary diolefin monomers include: CH (CH)2＝CH(CF2)4CH＝CH2、CH2＝CH(CF2)6CH＝CH2、CH2＝CH(CF2)8CH＝CH2、CF2＝CF-O-(CF2)2-O-CF＝CF2、CF2＝CF-O-(CF2)3-O-CF＝CF2、CF2＝CF-O-(CF2)4-O-CF＝CF2、CF2＝CF-O-(CF2)5-O-CF＝CF2、CF2＝CF-O-(CF2)6-O-CF＝CF2、CF2＝CF-CF2-O-(CF2)2-O-CF＝CF2、CF2＝CF-CF2-O-(CF2)3-O-CF＝CF2、CF2＝CF-CF2-O-(CF2)4-O-CF＝CF2、CF2＝CF-CF2-O-(CF2)4-O-CF＝CF2、CF2＝CF-CF2-O-(CF2)5-O-CF＝CF2、CF2＝CF-CF2-O-(CF2)6-O-CF＝CF2、CF2＝CF-CF2-O-(CF2)2-O-CF2-CF＝CF2、CF2＝CF-CF2-O-(CF2)3-O-CF2-CF＝CF2、CF2＝CF-CF2-O-(CF2)4-O-CF2-CF＝CF2、CF2＝CF-CF2-O-(CF2)5-O-CF2-CF＝CF2、CF2＝CF-CF2-O-(CF2)6-O-CF2-CF＝CF2、CF2＝CF-O-CF2CF2-CH＝CH2、CF2＝CF-(OCF(CF3)CF2)-O-CF2CF2-CH＝CH2、CF2＝CF-(OCF(CF3)CF2)2-O-CF2CF2-CH＝CH2、CF2＝CFCF2-O-CF2CF2-CH＝CH2、CF2＝CFCF2-(OCF(CF3)CF2)-O-CF2CF2-CH＝CH2、CF2＝CFCF2-(OCF(CF3)CF2)2-O-CF2CF2-CH＝CH2、CF2＝CF-CF2-CH＝CH2、CF2＝CF-O-(CF2)c-O-CF2-CF2-CH＝CH2(wherein c is an integer selected from 2 to 6), CF2＝CFCF2-O-(CF2)c-O-CF2-CF2-CH＝CH2(wherein c is an integer selected from 2 to 6), CF2＝CF-(OCF(CF3)CF2)b-O-CF(CF3)-CH＝CH2(wherein b is 0, 1 or 2), CF2＝CF-CF2-(OCF(CF3)CF2)b-O-CF(CF3)-CH＝CH2(wherein b is 0, 1 or 2), CH2＝CH-(CF2)n-O-CH＝CH2(wherein n is an integer of 1 to 10) and CF2＝CF-(CF2)a-(O-CF(CF3)CF2)b-O-(CF2)c-(OCF(CF3)CF2)f-O-CF＝CF2(wherein a is 0 or 1, b is 0, 1 or 2, c is 1,2, 3, 4, 5 or 6, and f is 0, 1 or 2).
In one embodiment of the present disclosure, a fluorinated block copolymer comprises: at least one A block polymeric unit, wherein each A block has a temperature greater than 0 ℃,5 ℃,10 ℃,15 ℃ or even 20 ℃; and a glass transition (Tg) temperature of less than 100 ℃, 90 ℃, 80 ℃, 70 ℃, 60 ℃ or even 50 ℃. The glass transition of the a and B blocks may be difficult to determine in DSC on a polymer gum, so the torsional rheology of the cured sample can be used to determine Tg. Two transitions were recorded when torsional rheology was performed on the cured samples using the method described in the examples section below: t isα(which is the first transition and is associated with the glass transition of the B block) and Tβ(which is the second, higher transition, associated with the glass transition of the A block).
In one embodiment, the weight average molecular weight of the semi-crystalline segment is at least 1000, 5000, 10000, or even 25000 daltons; and at most 400000, 600000 or even 800000 daltons.
In the present disclosure, the B block is a fluorinated segment derived from at least one fluorinated monomer and a nitrile-containing cure site monomer.
Exemplary nitrile containing cure site monomers include perfluoro (8-cyano-5-methyl-3, 6-dioxa-1-octene); CF2＝CFO(CF2)LCN, wherein L is an integer from 2 to 12; CF (compact flash)2＝CFO(CF2)uOCF(CF3) CN, wherein u is an integer from 2 to 6; CF (compact flash)2＝CFO[CF2CF(CF3)O]q(CF2O)yCF(CF3) CN, wherein q is an integer from 0 to 4, and y is an integer from 0 to 6; or CF2＝CF[OCF2CF(CF3)]rO(CF2)tCN, wherein r is 1 or 2, and t is an integer from 1 to 4; and derivatives and combinations of the foregoing. Exemplary nitrile containing cure site monomers include: CF (compact flash)2＝CFO(CF2)5CN、CF2＝CFOCF2CF(CF3)OCF2CF2CN、CF2＝CFOCF2CF(CF3)OCF2CF(CF3)CN、CF2＝CFOCF2CF2CF2OCF(CF3)CN、CF2＝CFOCF2CF(CF3)OCF2CF2CN; and combinations thereof.
(1) In one embodiment, the B block is a copolymer derived from VDF and at least one comonomer. The comonomer may be selected from: perfluorinated olefins containing 2-8 carbon atoms (such as TFE or HFP); halofluorinated olefins, wherein the halogen is chlorine, bromine and/or iodine containing from 2 to 8 carbon atoms (such as chlorotrifluoroethylene); fluorinated vinyl ethers such as perfluorinated vinyl ethers and perfluorinated allyl ethers as described above; non-fluorinated olefins containing 2 to 8 carbon atoms, such as ethylene or propylene. An exemplary B block composition comprises the following components: (a)45-85 wt% VDF, 15-45 wt% HFP and 0-30 wt% TFE; (b)50-80 wt% VDF, 5-50 wt% fluorinated vinyl ether such as PAVE and 0-20 wt% TFE 0-20%; and (c)20-30 wt% VDF, 10-30 wt% non-fluorinated olefin, 18-27 wt% HFP and/or PAVE, and 10-30 wt% TFE.
(2) In one embodiment, the B block is a copolymer derived from HFP and VDF. An exemplary B block composition comprises the following components: 25-65 wt% VDF and 15-60 wt% HFP; or even 35-60 wt% VDF and 25-50 wt% HFP. The other comonomer may be added in an amount in the range of at least 0.1 wt%, 0.5 wt%, 1 wt% or even 2 wt% and up to 5 wt%, 10 wt%, 15 wt%, 20 wt% or even 30 wt%. Such comonomers include perfluorovinyl ether and perfluoroallyl ether monomers as described above.
(3) In one embodiment, the B block is derived from HFP, VDF, and diolefin monomers, such as those described above. In one embodiment, the B block comprises from 25 to 65 weight percent VDF, from 15 to 60 weight percent HFP, and from 0.01 to 1 weight percent of a diolefin monomer; or even 35 to 60 weight percent VDF, 25 to 50 weight percent HFP and 0.02 to 0.5 weight percent diolefin monomer. Such diolefin monomers are described above. The other comonomer may be added in an amount in the range of at least 0.1 wt%, 0.5 wt%, 1 wt% or even 2 wt% and up to 5 wt%, 10 wt%, 15 wt%, 20 wt% or even 30 wt%. Such comonomers include perfluorovinyl ether and perfluoroallyl ether monomers as described above.
(4) In one embodiment, the B block is derived from TFE and a comonomer selected from the group consisting of: fluorinated olefins containing 2 to 8 carbon atoms (such as TFE, HFP, trifluoroethylene); halofluorinated olefins, wherein the halogen is chlorine, bromine and/or iodine containing from 2 to 8 carbon atoms (such as chlorotrifluoroethylene); fluorinated vinyl ethers such as perfluorinated vinyl ethers and perfluorinated allyl ethers as described above; non-fluorinated olefins containing 2 to 8 carbon atoms, such as ethylene or propylene. An exemplary B block composition comprises the following components: (a)50-80 wt% TFE and 20-50 wt% fluorinated vinyl ether; (b)45-65 wt.% TFE, 20-55 wt.% non-fluorinated olefin, and 0-30 wt.% VDF; and (c)32-60 wt.% TFE, 10-40 wt.% non-fluorinated olefin, and 20-40 wt.% fluorinated vinyl ether.
In one embodiment, the B block of the present disclosure is an amorphous segment, meaning that there is no long range order (i.e., in long range order, the arrangement and orientation of macromolecules beyond their nearest neighbors is understood). The amorphous segment has no crystalline character detectable by DSC. If studied under DSC, the B block will have no melting point or melt transition, enthalpy greater than 2 mJ/g according to DSC.
In another embodiment, the B block of the present disclosure is semi-crystalline, meaning that the block will have at least one melting point (T) greater than 60 ℃, 70 ℃, 80 ℃, or even 90 ℃, and up to 110 ℃, 120 ℃, 130 ℃, or even 150 ℃ when measured by DSCm) And a measurable enthalpy (e.g., greater than 2 mj/g).
In one embodiment, the modulus of the B block is such that it can be processed as an elastomer. In one embodiment, the B block has a modulus at 100 ℃ of less than 2.5MPa, 2.0MPa, 1.5MPa, 1MPa, or even 0.5MPa, as measured at a strain of 1% and a frequency of 1 Hz.
In the present disclosure, the a block and/or B block may be polymerized in the presence of a chain transfer agent and/or optionally other cure site monomers to introduce cure sites into the fluoropolymer, which may then be used in a subsequent crosslinking reaction.
In one embodiment, the chain transfer agent has the formula Y (CF)2)qY, wherein: (i) y is independently selected from Br or I, wherein optionally one Y is Cl, and (ii) q is an integer from 1 to 12, preferably 3-12. Exemplary perfluorinated iodocompounds include 1, 3-diiodoperfluoropropane, 1, 4-diiodoperfluorobutane, 1, 6-diiodoperfluorohexane, 1, 8-diiodoperfluorooctane, 1, 10-diiodoperfluorodecane, 1, 12-diiodoperfluorododecane, and mixtures thereof.
In one embodiment, the chain transfer agent is a fluorinated di-iodo ether compound of the formula:
Rf-CF(I)-(CX2)n-(CX2CXR)m-O-R”f-Ok-(CXR’CX2)p-(CX2)q-CF(I)-R’f
wherein
X is independently selected from F, H and Cl;
r is F or a partially or perfluorinated alkane comprising 1 to 3 carbons;
Rfand R'fIndependently selected from F and monovalent perfluoroalkanes having 1 to 3 carbons;
R”fis a divalent fluoroalkylene group having 1 to 5 carbons or a divalent fluoroalkylene ether group having 1 to 8 carbons and at least one ether linkage;
k is 0 or 1; and n, m, q and p are independently selected from integers from 0 to 5, with the proviso that when k is 0, n plus m is at least 1 and p plus q is at least 1.
Exemplary fluorinated di-iodo ether compounds include: I-CF2-CF2-O-CF2-CF2-I；I-CF2-CF2-O-(CF2)b-I, wherein b is an integer from 3 to 10; i- (CF)2)c-O-(CF2)b-I, wherein c is an integer from 3 to 10 and b is an integer from 3 to 10; ICF2-CF2-O-CF2-O-CF2-CF2-I；ICF2-CF2-O-CF2-(CF2)b-O-CF2-CF2I, wherein b is an integer from 1 to 5; ICF2-CF2-[O-CF2-(CF2)b]z-O-CF2-CF2I, wherein b is an integer from 1 to 5, z is an integer from 1 to 4; I-CF2-CH2-O-CF2-CF2-CF2I；I-CF2-CH2-CF2-O-CF2-CF2-CF2I；I-CF2-CHF-CF2-O-CF2-CF2-CF2I；ICF2-CF2-O-CF2-CFI-CF3；ICF2-CF2-(CF2)a-[O-CF-CF2]b-(O-[CF2]c)z-O[-CF2]d-CF2-CF2I, wherein a is an integer from 0 to 6, b is an integer from 0 to 5, c is an integer from 1 to 6, d is an integer from 0 to 6 and z is an integer from 0 to 6; ICF2-(CF2)a-(O-CF2CF(CF3))b-O-(CF2)c-O-(CF2-CF-O)d-(CF2)z-O-CF2CF2-I, wherein a is an integer from 0 to 6, b is an integer from 0 to 5, c is an integer from 1 to 6, d is an integer from 0 to 5 and z is an integer from 0 to 5; and I-CF2-(CF2)a-O-(CF2)b-O-CF2-CF(CF3) -I, wherein a is an integer from 1 to 5 and b is an integer from 1 to 5; such fluorinated di-iodo ether compounds are disclosed in WO 2015/134435(Hintzer et al), which is incorporated herein by reference.
In one embodiment, the cure site monomer may be selected from one or more compounds of the formula: (a) CX2Cx (z), wherein: (i) each X is independently H or F; and (ii) Z is I, Br or Rf-U, wherein U is I or Br, and RfIs a perfluorinated alkylidene group optionally containing an O atom. In addition, non-fluorinated bromoolefins or iodoolefins, such as ethylene iodide and allyl iodide, may be used. In some embodiments, the cure site monomer is derived from one or more compounds selected from the group consisting of: CF (compact flash)2＝CFCF2I、ICF2CF2CF2CF2I、CF2＝CFCF2CF2I、CF2＝CFOCF2CF2I、CF2＝CFOCF2CF2CF2I、CF2＝CFOCF2CF2CH2I、CF2＝CFCF2OCH2CH2I、CF2＝CFO(CF2)3–-OCF2CF2I、CF2＝CFCF2Br、CF2＝CFOCF2CF2Br、CF2＝CFCl、CF2＝CFCF2Cl and combinations thereof.
In one embodiment, the amount of nitrile cure site monomer used will be in a range of at least 0.01, 0.05, 0.1, 0.5, or even 0.75 weight percent and up to 1,2, 3,5, or even 10 weight percent, as compared to the weight of the B block.
In one embodiment of the present disclosure, a fluorinated block copolymer comprises: at least one B block polymerized unit, wherein each B block has a Tg temperature of less than 0 ℃, -10 ℃, -20 ℃, or even-30 ℃. As mentioned above, the glass transition of the a and B blocks may be difficult to determine using DSC, so the Tg of a particular block can be determined using torsional rheology on the cured sample.
The Tg of the polymerized block (i.e., the A block or the B block) can be estimated by using the Fox equation based on the Tg's of the constituent monomers and their weight percentages. The Fox formula is described in the articles entitled "methods for the preparation of polymer chemistry" by w.r. sorenson and t.w.campbell, "indirect science: new York (1968), p.209 (W.R. Sorenson and T.W Campbell's text entry, "preliminary Methods of Polymer Chemistry," Interscience, New York (1968) p.209). Specific Tg values for suitable homopolymers are available from sections in the polymer handbook, third edition, p.peyser, editors by j.brandrup and e.h.immergut, Wiley: new York (1989), pages V-209 to VI-277 (P.Peyser's chapter in polymer handbook, 3)rded., edited by J.Brandrup and E.H.Immergut, Wiley, New York (1989) pages V-209through VI-227). Alternatively, the Tg of the polymeric block can be measured by Differential Scanning Calorimetry (DSC) or Dynamic Mechanical Analysis (DMA) analysis of the polymer comprising the constituent monomers and their weight percentages.
In one embodiment, the weight average molecular weight of the B block segment is at least 5000, 10000 or even 25000; and at most 400000, 600000 or even 800000.
In the fluorinated block copolymers of the present disclosure, the a and B blocks are covalently bonded together. In one embodiment, the a blocks are directly attached to the B blocks (in other words, the carbon atoms of the a blocks are covalently bonded to the carbon atoms of the B blocks). In one embodiment, the block copolymer of the present disclosure is a linear block copolymer. The linear block copolymer may be divided into a diblock ((A-B) structure), a triblock ((A-B-A) structure), and a multiblock (- (A-B)n-structure) and combinations thereof. In another embodiment, the block copolymers of the present disclosure may be branched copolymers, for example, where the branches extend from the polymer backboneExtended comb polymers.
In one embodiment of the present disclosure, the fluorinated block copolymer comprises at least one B block and at least two a blocks, wherein B is a mid-block and a is an end-block. In another embodiment of the present disclosure, the fluorinated block copolymer comprises at least one a block and at least two B blocks, wherein a is a mid-block and B is an end-block. The compositions of the end blocks need not be identical to each other, but preferably they are similar in composition.
In one embodiment, the fluorinated block copolymer consists essentially of at least one a block and at least one B block. In other words, the fluorinated block copolymer comprises only a and B block segments, however, the ends of the polymer chain at which the polymerization reaction is terminated may comprise different groups (a pair of atoms in size) due to the initiator and/or chain transfer agent used during polymerization.
In some embodiments, more than two different blocks are used. In one embodiment, multiple blocks having different weight average molecular weights or multiple blocks having different concentrations of block polymeric units may be used. In one embodiment, a third block may be present that is derived from at least one different monomer.
In one embodiment of the present disclosure, the fluorinated block copolymer has a Tg of less than 0 ℃, -5 ℃, -10 ℃, -15 ℃, -20 ℃, or even-25 ℃, as determined by DSC, as described in the examples section below.
The fluorinated block copolymers of the present disclosure can be prepared by various known methods, so long as the a and B blocks are covalently bonded to each other in block or graft form.
In one embodiment, the B block may be prepared by iodine transfer polymerization, as described in U.S. Pat. No. 4,158,678(Tatemoto et al). For example, during emulsion polymerization, a free radical initiator and an iodine chain transfer agent are used to produce, for example, an amorphous polymer latex. The free radical polymerization initiator used to prepare the amorphous segments may be the same as those known in the art for polymerization of fluoroelastomers. Examples of such initiators are organic and inorganic peroxides and azo compounds. Typical examples of initiators are persulfates, peroxycarbonates, peroxyesters, and the like. In one embodiment, Ammonium Persulfate (APS) is used alone or in combination with a reducing agent such as sulfite. Typically, the iodine chain transfer agent is used in an amount of 0.01 to 1 weight percent based on the total weight of the polymer. Exemplary diiodo compounds include: 1, 3-diiodoperfluoropropane, 1, 4-diiodoperfluorobutane, 1, 3-diiodo-2-chloroperfluoropropane, 1, 5-diiodo-2, 4-dichloroperfluoropentane, 1, 6-diiodoperfluorohexane, 1, 8-diiodoperfluorooctane, 1, 12-diiodoperfluorododecane, 1, 16-diiodoperfluorohexadecane, diiodomethane and 1, 2-diiodoethane. For emulsion polymerization, various emulsifiers can be used. From the viewpoint of suppressing chain transfer reaction against emulsifier molecules generated during polymerization, a desirable emulsifier is a carboxylate having a fluorocarbon chain or a fluoropolyether chain. In one embodiment, the amount of emulsifier is from about 0.05 to about 2 wt%, or even from 0.2 to 1.5 wt%, based on the added water. The nitrile containing cure site monomer may be added to the polymerization in a batch or continuous manner as is known in the art. The latex thus obtained comprises an amorphous polymer having iodine atoms which become the starting point of block copolymerization of semi-crystalline segments. For the latex thus obtained, the monomer composition can be varied and block copolymerization of semi-crystalline segments onto amorphous polymers can be carried out.
In one embodiment, fluorinated emulsifiers with improved environmental characteristics may be used during the polymerization of the block copolymers disclosed herein. In one embodiment, the fluorinated emulsifier corresponds to the general formula:
Y-Rf-Z-M
wherein Y represents hydrogen, Cl or F; rfRepresents a linear or branched partially fluorinated alkylidene group having from 4 to 10 carbon atoms and optionally comprising catenary oxygen atoms; z represents COO-Or SO3 -And M represents a hydrogen ion, an alkali metal ion or an ammonium ion. Exemplary fluorinated emulsifiers may have the general formula:
[Rf-O-L-COO-]iXi+
wherein L represents a straight chain or a branched chainOr a partially or fully fluorinated alkylidene group or an aliphatic hydrocarbon group, RfDenotes a linear or branched, partially or fully fluorinated aliphatic group or a linear or branched, partially or fully fluorinated group doped with one or more oxygen atoms, Xi+Represents a cation having a valence i, and i is 1,2 or 3. In one embodiment, the emulsifier is selected from CF3-O-(CF2)3-O-CHF-CF2-COOH and salts thereof. Specific examples are described in U.S. patent 7671112(Hintzer et al), which is incorporated herein by reference. Exemplary emulsifiers include: CF (compact flash)3CF2OCF2CF2OCF2COOH、CHF2(CF2)5COOH、CF3(CF2)6COOH、CF3O(CF2)3OCF(CF3)COOH、CF3CF2CH2OCF2CH2OCF2COOH、CF3O(CF2)3OCHFCF2COOH、CF3O(CF2)3OCF2COOH、CF3(CF2)3(CH2CF2)2CF2CF2CF2COOH、CF3(CF2)2CH2(CF2)2COOH、CF3(CF2)2COOH、CF3(CF2)2OCF(CF3)CF2OCF(CF3)COOH、CF3(CF2)2(OCF2CF2)4OCF(CF3)COOH、CF3OCF2CF(CF3)OCF(CF3)COOH、C3F7OCF(CF3)COOH、CF3CF2O(CF2CF2O)3CF2COOH and salts thereof.
In one embodiment, a non-ionic, non-fluorinated saturated emulsifier may be used during the polymerization of the block copolymers disclosed herein. Such nonionic, nonfluorinated emulsifiers include polycaprolactone, silicone, polyethylene/polypropylene glycol (cyclodextrin), carbosilanes, and sugar-based emulsifiers. Other examples include polyether alcohols, sugar-based emulsifiers or hydrocarbon-based emulsifiers, wherein the long-chain units may contain from 4 to 40 carbon atoms. In one embodiment, non-fluorinated, saturated anionic emulsifiers may be used during the polymerization of the block copolymers disclosed herein. Such non-fluorinated anionic emulsifiers include polyvinylphosphinic acid, polyacrylic acid, polyvinylsulfonic acid, and alkylphosphonic acids (e.g., alkylphosphates, hydrocarbon anionic surfactants, as described, for example, in U.S. Pat. Nos. 7521513 and 6512063(Tang), both of which are incorporated herein by reference). These emulsifiers and their use in polymerization reactions are described in WO 2016/137851(Jochum et al), which is incorporated herein by reference.
In one embodiment, the fluorinated block copolymers of the present disclosure may be crosslinked. Crosslinking of the resulting fluorinated block copolymer can be carried out using curing systems known in the art such as peroxide curing agents, 2, 3-dimethyl-2, 3-diphenylbutane and other free radical initiators such as azo compounds, as well as other curing systems such as polyols, and polyamine curing systems.
Peroxide curatives include organic or inorganic peroxides. Organic peroxides are preferred, especially those that do not decompose at the dynamic mixing temperatures.
Crosslinking using peroxide can be generally performed by using an organic peroxide as a crosslinking agent and, if necessary, a polyolefin crosslinking aid including, for example, diolefin (such as CH)2＝CH(CF2)6CH＝CH2And CH2＝CH(CF2)8CH＝CH2) Diallyl ethers of glycerol, triallyl phosphate, diallyl adipate, diallyl melamine and triallyl isocyanurate (TAIC), fluorinated TAIC comprising fluorinated olefinic bonds, tri (methyl) allyl isocyanurate (TMAIC), tri (methyl) allyl cyanurate, poly-triallyl isocyanurate (poly-TAIC), xylylene-bis (diallyl isocyanurate) (XBD) and N, N' -m-phenylene bismaleimide.
Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2, 5-di-methyl-2, 5-di-t-butylperoxyhexane, 2, 4-dichlorobenzoyl peroxide, 1-bis (t-butylperoxy) -3,3, 5-trimethylchlorohexane, t-butylperoxyisopropyl carbonate (TBIC), t-butylperoxy 2-ethylhexyl carbonate (TBEC), t-amylperoxy 2-ethylhexyl carbonate, t-hexylperoxy isopropyl carbonate, carbon peroxy acid, O '-1, 3-propanediyl OO, OO' -bis (1, 1-dimethylethyl) ester, t-butylperoxybenzoate, t-hexylperoxy-2-ethylhexanoate, O, n-butylperoxy-2-dimethylhexyl carbonate, O, n-butyl peroxy-2-dimethylhexyl carbonate, n-butyl peroxy-2-methyl peroxy-ethyl hexanoate, n-butyl peroxy-2-ethyl peroxy-carbonate, n-butyl peroxy-2-ethyl hexanoate, n-butyl peroxy-2-ethyl-carbonate, n-butyl peroxy-2-ethyl-butyl peroxy-carbonate, n-2-butyl peroxy-ethyl-carbonate, O-butyl peroxy-2-butyl peroxy-carbonate, O-butyl peroxy-carbonate, O-butyl peroxy-2-butyl peroxy-carbonate, O-butyl peroxy-carbonate, O-butyl peroxy-carbonate, O-butyl peroxy-butyl carbonate, O-butyl peroxy-2-butyl peroxy-butyl carbonate, O-butyl carbonate, O-butyl peroxy-butyl carbonate, O-butyl peroxy-butyl carbonate, O-butyl carbonate, O-butyl peroxy-butyl carbonate, O-butyl carbonate, O-butyl carbonate, and, T-butyl peroxy-2-ethylhexanoate, bis (4-methylbenzoyl) peroxide, lauryl peroxide, and cyclohexanone peroxide. Other suitable peroxide curatives are listed in U.S. Pat. No.5,225,504(Tatsu et al). The amount of peroxide curing agent used will generally be from 0.1 to 5 parts by weight per 100 parts of fluorinated block copolymer, preferably from 1 to 3 parts by weight per 100 parts of fluorinated block copolymer. Other conventional free radical initiators are suitable for use with the present disclosure.
Examples of azo compounds that can be used to cure the fluorinated block copolymers of the present disclosure are those having high decomposition temperatures. In other words, they decompose above the upper use temperature of the resulting product. Such azo compounds can be found, for example, in encyclopedia of Polymer Materials (Polymer Materials encyclopedia), edited by J.C.Salamone, CRC Press, N.Y. (CRC Press Inc.), 1996, Vol.1, p.432-440.
Generally by using polyol compounds as crosslinking agents; crosslinking aids such as ammonium salts, phosphonium salts, and iminium salts; and hydroxides or oxides of divalent metals such as magnesium, calcium or zinc. Examples of the polyol compound include bisphenol AF, bisphenol a, bisphenol S, dihydroxybenzophenone, hydroquinone, 2,4, 6-trimercapto-S-triazine, 4' -thiodiphenol, and metal salts thereof.
Crosslinking using polyamines is generally performed by using polyamine compounds as crosslinking agents and oxides of divalent metals such as magnesium, calcium or zinc. Examples of the polyamine compound or polyamine compound precursor include hexamethylenediamine and its carbamate, 4 '-bis (aminocyclohexyl) methane and its carbamate, and N, N' -biscinnamaldehyde-1, 6-hexamethylenediamine.
The crosslinking agent (and the crosslinking assistant, if used) may each be used in a conventionally known amount, and the amount to be used may be appropriately determined by one skilled in the art. Each of these components participating in crosslinking may be used, for example, in an amount of about 1 part by mass or more, about 5 parts by mass or more, about 10 parts by mass or more, or about 15 parts by mass or more, and about 60 parts by mass or less, about 40 parts by mass or less, about 30 parts by mass or less, or about 20 parts by mass or less per 100 parts by mass of the fluorinated block copolymer. The total amount of the components participating in crosslinking may be, for example, about 1 part by mass or more, about 5 parts by mass or more, or about 10 parts by mass or more, and about 60 parts by mass or less, about 40 parts by mass or less, or about 30 parts by mass or less per 100 parts by mass of the fluorinated block copolymer.
In one embodiment, a dual cure or multi-cure system is used, wherein at least two different cure systems are used. For example, peroxide cure systems and bisphenol cure systems or peroxide cure systems and triazine cure systems. Such multi-cure systems may provide enhanced physical properties and/or ease of handling.
For example, conventional adjuvants such as, for example, acid acceptors, fillers, processing aids, or colorants may be added to the composition for the purpose of enhancing strength or imparting functionality.
For example, an acid acceptor may be used to promote cure stability and thermal stability of the composition. Suitable acid acceptors can include magnesium oxide, lead oxide, calcium hydroxide, lead hydrogen phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite, basic stearates, magnesium oxalate, or combinations thereof. The acid acceptor is preferably used in an amount ranging from about 1 part to about 20 parts per 100 parts by weight of the fluorinated block copolymer.
The filler comprises: organic or inorganic fillers, e.g. clays, Silica (SiO)2) Alumina, iron oxide red, talc, diatomaceous earth, barium sulfate, wollastonite (CaSiO)3) Carbon, carbonCalcium carbonate (CaCO)3) Calcium fluoride, titanium oxide, iron oxide and carbon black fillers, polytetrafluoroethylene powder, PFA (TFE/perfluorovinyl ether copolymer) powder, conductive fillers, heat-dissipating fillers, and the like may be added to the composition as optional components. Those skilled in the art will be able to select the particular filler in the required amount to achieve the desired physical characteristics of the cured compound. The filler component may produce a compound capable of maintaining a preferred elasticity and physical tension (as indicated by elongation and tensile strength values) while maintaining desired properties such as recoil at lower temperatures (TR-10). In one embodiment, the composition comprises less than 40, 30, 20, 15, or even 10 weight percent filler.
The fluorinated block copolymer composition is mixed with a curing agent and optionally conventional adjuvants. In one embodiment, the process for mixing the block copolymer of the present disclosure with the curing agent and optional adjuvants is performed in a manner similar to elastomers, such as, for example, kneading using a two-roll, pressure kneader or banbury mixer for rubber. In another embodiment, the process for mixing the block copolymer of the present disclosure with the curing agent and optional adjuvants is performed in a manner similar to plastics, such as by extrusion or injection molding.
The mixture can then be processed and shaped, such as by extrusion or molding, to form articles of various shapes, such as sheets, hoses, hose liners, O-rings, gaskets, packings, or seals comprised of the compositions of the present disclosure. The shaped article can then be heated to cure the gum composition and form a cured elastomeric article.
The compounded mixture is typically pressurized (i.e., press cured) at a temperature of about 120-220 deg.C, or even at a temperature of about 140-200 deg.C for a period of about 1 minute to about 15 hours, typically about 1 minute to 15 minutes. Pressures of about 700-. The mold may first be coated with a release agent and pre-baked.
The molded vulcanizate may be post-cured in an oven at a temperature of about 140 ℃ to 240 ℃, or even about 160 ℃ to 230 ℃ for a period of about 1 to 24 hours or more, depending on the cross-sectional thickness of the specimen. For thick sections, the temperature during post-cure is typically raised gradually from the lower end of the range to the desired maximum temperature. The maximum temperature used is preferably about 260 c and is maintained at this value for a period of about 1 hour or more.
The fluorinated block copolymers of the present disclosure can be used in articles such as hoses, seals (e.g., gaskets, O-rings, packer elements, blowout preventers, valves, etc.), stators, or sheets. These compositions may or may not be post-cured.
By utilizing the high stretch and high modulus provided by the a block and/or nitrile cure site monomers, fluorinated block copolymers with good toughness (e.g., high tensile strength) can optionally be achieved.
The fluorinated block copolymers of the present disclosure balance the toughness imparted by the a block and/or nitrile cure site monomers with the viscosity (and optionally flexibility) imparted by the B block. This equilibration of the A and B blocks produces fluorinated block copolymers that can be processed as conventional elastomers (e.g., polymers that can be processed with a two-roll mill or internal mixer) or as conventional plastics, depending on the modulus of the resulting block copolymer. Mill blending is one method used by rubber manufacturers to mix polymer gums with the necessary curatives and/or additives. In order to grind the blend, the curable composition must have sufficient modulus. In other words, it is not so soft that it sticks to the mill, and not so hard that it cannot be attached to the mill. In one embodiment, to be processed as a conventional elastomer, the fluorinated block copolymers of the present disclosure should have a modulus at 100 ℃ of at least 0.1, 0.3, or even 0.5MPa (megapascals) and at most 2.5, 2.2, or even 2.0MPa, as measured at 1% strain and 1Hz (hertz) frequency. The amount of A block to B block used in the fluorinated block copolymer can vary depending on the characteristics of the individual polymer segments. For example, if the a block has high crystallinity, overall less a block is used in the fluorinated block copolymer. Thus, storage modulus is a useful property to consider when using less semi-crystalline segments with high crystallinity in a block copolymer relative to more semi-crystalline segments with lower crystallinity. By adding more A blocks to the fluorinated block copolymer, better stretching is achieved and the polymer retains properties at high temperatures. However, if too much A block is used, the composition cannot be processed as an elastomer.
In one embodiment, the fluorinated block copolymers of the present disclosure have a temperature of at least 100 ℃, 110 ℃, 150 ℃, or even 175 ℃; and a melting point of at most 275 ℃, 250 ℃ or even 200 ℃. It is believed that the melting point of the fluorinated block copolymer is based on the melting point of the semi-crystalline segment, since amorphous polymers do not have melting points. In one embodiment, the melting point of the block copolymer is greater than the upper service temperature of the resulting article to maximize the reinforcing effect of the a block.
In one embodiment, the fluorinated block copolymers of the present disclosure have a temperature of greater than-40 ℃, -30 ℃, or even-20 ℃ as measured by DSC; and a Tg of at most 15 ℃,10 ℃,0 ℃ or even-5 ℃ as described in the examples section below. Both the a and B blocks will have Tg. Generally, the Tg of the B block is believed to be responsible for the reported Tg of the block copolymer.
In one embodiment, the fluorinated block copolymers of the present disclosure have a melt flow rate as measured by ASTM D1238-13 "standard test method for melt flow rate of thermoplastics by extrusion of plastomers" of greater than 5, 10, 20, or even 30 with a 5Kg load at 230 ℃; and a melt flow index of at most 40, 50, 60, 70, 80, or even 90.
Depending on the method of preparing the fluorinated block copolymer and/or the iodine-containing cure site monomer and/or the iodine-containing chain transfer agent, the fluorinated block copolymer may comprise iodine. In one embodiment, the fluorinated block copolymer comprises at least 0.05 wt%, 0.1 wt%, or even 0.2 wt%, based on the weight of the fluorinated block copolymer; and up to 0.5 wt%, 0.8 wt% or even 1 wt% iodine.
The fluorinated block copolymers of the present disclosure can have a weight average molecular weight (Mw) of at least 50,000 daltons, at least 100,000 daltons, at least 300,000 daltons, at least 500,000 daltons, at least 750,000 daltons, at least 1,000,000 daltons, or even at least 1,500,000 daltons and a molecular weight not so high as to cause premature gelation of the fluorinated block copolymer.
The fluorinated block copolymers of the present disclosure, in which the a and B blocks are covalently bonded together, have properties such as higher tensile strength and optionally improved compression set that are superior to mixtures (or blends) of the two individual polymers.
The fluorinated block copolymers of the present disclosure have been found to have good tensile strength and 100% modulus. Surprisingly, it has additionally been found that the fluorinated block copolymers of the present disclosure have good compressive set. Compression set is the deformation of the polymer remaining once the force is removed. Generally, lower compression set values are better (i.e., less material deformation). Generally, plastics (including semi-crystalline morphologies) do not have good compression set. Thus, it is surprising that fluorinated block copolymers comprising semi-crystalline segments have good compression set. It is also surprising that the fluorinated block copolymers of the present disclosure retain their properties at high temperatures.
Exemplary embodiments of the present disclosure include, but should not be limited to, the following:
embodiment 1. a curable composition comprising:
a fluorinated block copolymer having
(a) At least one A block, wherein the A block is a semi-crystalline segment comprising repeating divalent monomer units derived from at least one fluorinated monomer;
(b) at least one B block, wherein the B block is a segment comprising repeating divalent monomer units derived from at least one fluorinated monomer and a nitrile-containing cure site monomer;
embodiment 2. the curable composition of embodiment 1, wherein the nitrile containing cure site monomer comprises at least one of: CF (compact flash)2＝CFO(CF2)5CN、CF2＝CFOCF2CF(CF3)OCF2CF2CN、CF2＝CFOCF2CF(CF3)OCF2CF(CF3)CN、CF2＝CFOCF2CF2CF2OCF(CF3)CN、CF2＝CFOCF2CF(CF3)OCF2CF2CN, and combinations thereof.
Embodiment 3. the curable composition of any of the preceding embodiments, wherein the a block is derived from TFE and less than 5 wt% comonomer.
Embodiment 4. the curable composition of any one of embodiments 1 to 2, wherein the a block is derived from TFE, HFP, and VDF.
Embodiment 5. the curable composition of embodiment 4 wherein the a block comprises repeating divalent monomer units further derived from at least one of perfluorinated vinyl ether monomers and perfluorinated allyl ether monomers.
Embodiment 6. the curable composition of embodiment 5, wherein the perfluorinated vinyl ether is selected from at least one of: perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE), perfluoro (n-propyl vinyl) ether (PPVE-1), perfluoro-2-propoxypropyl vinyl ether (PPVE-2), perfluoro-3-methoxy-n-propyl vinyl ether, perfluoro-2-methoxy-ethyl vinyl ether, CF2＝CFOCF2OCF3、CF2＝CFOCF2OCF2CF3And CF3-(CF2)2-O-CF(CF3)-CF2-O-CF(CF3)-CF2-O-CF＝CF2。
Embodiment 7. the curable composition of embodiment 4, wherein the perfluorinated allyl ether is selected from at least one of: perfluoro (methallyl) ether (CF)2＝CF-CF2-O-CF3) Perfluoro (ethyl allyl) ether, perfluoro (n-propyl allyl) ether, perfluoro-2-propoxypropyl allyl ether, perfluoro-3-methoxy-n-propyl allyl ether, perfluoro-2-methoxy-ethyl allyl ether, perfluoro-methoxy-methyl allyl ether, and CF3-(CF2)2-O-CF(CF3)-CF2-O-CF(CF3)-CF2-O-CF2CF＝CF2。
Embodiment 8 the curable composition of any one of the previous embodiments, wherein the fluorinated block copolymer has a melting point of at least 100 ℃ and at most 275 ℃.
Embodiment 9 the curable composition of any one of the previous embodiments, wherein the B block is derived from at least VDF and a nitrile containing cure site monomer.
Embodiment 10 the curable composition of any of the preceding embodiments, wherein the B block is derived from at least VDF, HFP, and a nitrile containing cure site monomer.
Embodiment 11 the curable composition of embodiment 10, wherein the B block segment further comprises repeating divalent monomer units derived from TFE, halogenated cure site monomer, perfluorovinyl ether monomer, perfluoroallyl ether monomer, and combinations thereof.
Embodiment 12 the curable composition of embodiment 11, wherein the halogenated cure site monomer is selected from at least one of: CF (compact flash)2＝CFCF2I、CF2＝CFCF2CF2I、CF2＝CFOCF2CF2I、CF2＝CFOCF2CF2CF2I、CF2＝CFOCF2CF2CH2I、CF2＝CFCF2OCH2CH2I、CF2＝CFO(CF2)3–-OCF2CF2I、CF2＝CFCF2Br、CF2＝CFOCF2CF2Br、CF2＝CFCl、CF2＝CFCF2Cl and combinations thereof.
Embodiment 13 the curable composition of any of the preceding embodiments, wherein the B block is semi-crystalline.
Embodiment 14. the curable composition of any one of embodiments 1 to 12, wherein the B block is amorphous.
Embodiment 15 the curable composition of any of the preceding embodiments, wherein the Tg of the a block is greater than 0 ℃ and less than 80 ℃.
Embodiment 16 the curable composition of any of the preceding embodiments, wherein the Tg of the B block is less than 0 ℃.
Embodiment 17. the curable composition of any of the preceding embodiments, wherein at least one of the following is derived from a diolefin monomer: an A block, a B block, or both an A block and a B block, the diolefin monomer having the formula
Figure BDA0002134695010000251
Wherein R is1、R2、R3、R4、R5And R6Independently an H, C1-C5 alkyl group or a C1-C5 fluorinated alkyl group; and Z is a linear or branched, optionally oxygen-containing and optionally fluorinated, alkylidene or cycloalkylidene C1-C18 group.
Embodiment 18 the curable composition of embodiment 17, wherein the diolefin monomer is at least one of: CH2 ═ CH (CF)2)6CH＝CH2And CH2＝CH(CF2)8CH＝CH2。
Embodiment 19. the curable composition of any of the preceding embodiments, wherein the fluorinated block copolymer comprises from about 0.05 wt% to about 1 wt% iodine, based on the weight of the fluorinated block copolymer.
Embodiment 20. the curable composition of any of the preceding embodiments, further comprising a peroxide cure system.
Embodiment 21. the curable composition of any of the preceding embodiments, further comprising a polyol cure system.
Embodiment 22. a cured article derived from the curable composition of any of the preceding embodiments.
Embodiment 23 the cured article of embodiment 22, wherein the article is a packer, O-ring, seal, gasket, hose, or sheet.
Embodiment 24. the curable composition of any of embodiments 1 to 21, wherein the fluorinated block copolymer has a glass transition temperature of less than-20 ℃.
Examples
Unless otherwise indicated, all parts, percentages, ratios, and the like in the examples and the remainder of the specification are by weight, and all reagents used in the examples were obtained (or are obtainable) from common chemical suppliers such as, for example, Sigma-Aldrich Company, Saint Louis, Missouri, or may be synthesized by conventional methods.
These abbreviations are used in the following examples: phr is parts per hundred rubber; rpm is the revolutions per minute; g is gram; kg is kg; min is minutes; h is h; the temperature is equal to centigrade degree; MPa ═ MPa; psi pounds per square inch; Hz-Hz; wt is weight; mm is millimeter; in is inch; lb in pounds and dNm in newton meters.
Method
Melting point and glass transition temperature
Melting Point (T)m) And glass transition temperature (T)g) Determined by differential scanning calorimetry (DSC, Q2000 of TA Instruments, New Castle, DE) in newcasel, tera) under a stream of nitrogen. The sample amount was 5 mg. + -. 0.25 mg. The DSC thermogram was obtained from the second heating of the heating/cooling/heating cycle. The first thermal cycle was started at-85 ℃ and increased to 300 ℃ at a rate of 10 ℃/min. The cooling cycle starts from the final temperature of the first heating cycle and cools to-85 ℃ at 10 ℃/min. The second thermal cycle was started at-85 ℃ and increased back to 300 ℃ at a rate of 10 ℃/min. The results are reported in table 1.
Modulus of elasticity
The modulus at 100 ℃ was determined from the storage modulus obtained from ASTM 6204-07 at 1% strain and a frequency of 1Hz using a rheometer (RPA 2000, Alpha technologies, Akron, OH) from Alpha technologies, Inc. of Akron, Ohio. The results are reported in table 1.
Curing rheology
Cured rheology tests were performed using uncured compounded samples using a rheometer (PPA 2000, Alpha technologies, Akron, OH) at 177 ℃, no preheat, 12 minute elapsed time, and 0.5 degree arc according to ASTM D5289-93 a. Measurement of not achieving plateau or maximum Torque (M)H) The minimum torque (M) obtained in a specified period of timeL) And the highest torque. Torque increases in excess of M were also measuredLTime of 2 units (t)s2) Torque up to ML+0.1(MH-ML) Time (t' 10) at which the torque reaches a value equal to ML+0.5(MH-ML) Time (t' 50) and torque reaching ML+0.9(MH-ML) Time (t' 90). The results are reported in table 2.
Physical Properties
O-rings having a cross-sectional thickness of 0.139 inch (3.5mm) and sheets having a thickness of 2.0mm were molded using uncured compounded samples and press cured, followed by post-curing as described in table 2. Dumbbell specimens were cut from the sheets and tested for physical properties similar to the procedure disclosed in ASTM D412-06a (2013). Tensile strength at break, elongation at break, 50% modulus and 100% modulus were recorded. The 50% modulus and 100% modulus were determined by tensile strength at 50% elongation and 100% elongation, respectively. The O-rings were subjected to a compression set test with an initial deflection of 25% in a procedure similar to that disclosed in ASTM 395-89 method B. The results are reported in table 2.
Material table
Figure BDA0002134695010000271
Figure BDA0002134695010000281
Preparation example 1(PE-1)
B block (B): a40 liter reactor was charged with 22500g of deionized water and heated to 80 ℃. The stirrer speed was then brought to 350rpm, and 40g of potassium phosphate, 140g of 1, 4-diiodooctafluorobutane, 14.6g of MV5CN, 330g of emulsifier and 20g of APS were then added. The reaction was rinsed into the reactor using 2500g of deionized water. The vacuum was broken with HFP. Immediately after this addition, the reactor was pressurized with an HFP/VDF ratio of 0.88 and a TFE/VDF ratio of 1.0 until the reactor reached a pressure of 1.5 MPa. Once this pressure was reached, the monomer ratio was changed to 1.24 for HFP/VDF and 0.73 for TFE/VDF. The reaction was run until 25% solids was reached, stopped, and left in the reactor.
A block: the latex from the above B block still in the reactor was then brought to 60 ℃, while the reactor was at that temperature, the stirrer speed was set to 350rpm and the vacuum was broken with nitrogen. The reactor was brought to a pressure of 1.6MPa using an HFP/VDF ratio of 0.768 and a TFE/VDF ratio of 8.068. The reaction was run at the same rate until 30% solids was reached. The latex was then coagulated using a 1.25% magnesium chloride solution in deionized water and oven dried at 130 ℃ for 32 hours.
The fluorinated block copolymer has a Tg of-11 ℃ and a Tm of 266 ℃ as determined by DSC. The theoretical ratio of B blocks to A blocks is 80: 20.
Preparation example 2(PE-2)
B block (B): a40 liter reactor was charged with 22500g of deionized water and heated to 80 ℃. The stirrer speed was then brought to 350rpm, and then 40g of potassium phosphate, 140g of 1, 4-diiodooctafluorobutane, 7.3g of MV5CN, 330g of emulsifier and 20g of APS were added. The reaction was rinsed into the reactor using 2500g of deionized water. The vacuum was broken with HFP. Immediately after this addition, the reactor was pressurized with an HFP/VDF ratio of 0.88 and a TFE/VDF ratio of 1.0 until the reactor reached a pressure of 1.5 MPa. Once this pressure was reached, the monomer ratio was changed to 1.24 for HFP/VDF and 0.73 for TFE/VDF. The reaction was run until 25% solids was reached, the reaction was stopped, and the latex was left in the reactor.
A block: the latex from the above B block still in the reactor was then brought to 60 ℃. Once at this temperature, 7.3g MV5CN was added. While the reactor was at this temperature, the stirrer speed was set to 350rpm and the vacuum was broken with nitrogen. The reactor was brought to a pressure of 1.6MPa using an HFP/VDF ratio of 0.768 and a TFE/VDF ratio of 8.068. The reaction was run at the same rate until 30% solids was reached. The latex was then coagulated using a 1.25% magnesium chloride solution in deionized water and oven dried at 130 ℃ for 32 hours.
The fluorinated block copolymer has a Tg of-11 ℃ and a Tm of 249 ℃ as determined by DSC. The theoretical ratio of B blocks to A blocks is 80: 20.
Example 3(PE-3)
B block (B): a40 liter reactor was charged with 22500g of deionized water and heated to 80 ℃. The stirrer speed was then brought to 350rpm, and then 40g of potassium phosphate, 140g of 1, 4-diiodooctafluorobutane, 7.3g of MV5CN, 10g of MV32I, 330g of emulsifier and 20g of APS were added. The reaction was rinsed into the reactor using 2500g of deionized water. The vacuum was broken with HFP. Immediately after this addition, the reactor was pressurized with an HFP/VDF ratio of 0.88 and a TFE/VDF ratio of 1.0 until the reactor reached a pressure of 1.5 MPa. Once this pressure was reached, the monomer ratio was changed to 1.24 for HFP/VDF and 0.73 for TFE/VDF. The reaction was run until 25% solids was reached, stopped, and left in the reactor.
A block: the latex from the above B block still in the reactor was then brought to 60 ℃, while the reactor was at that temperature, the stirrer speed was set to 350rpm and the vacuum was broken with nitrogen. The reactor was brought to a pressure of 1.6MPa using an HFP/VDF ratio of 0.768 and a TFE/VDF ratio of 8.068. The reaction was run at the same rate until 30% solids was reached. The latex was then coagulated using a 1.25% magnesium chloride solution in deionized water and oven dried at 130 ℃ for 32 hours.
The fluorinated block copolymer has a Tg of-11 ℃ and a Tm of 254 ℃ as determined by DSC. The theoretical ratio of B blocks to A blocks is 80: 20.
Example 4(PE-4)
B block (B): a40 liter reactor was charged with 22500g of deionized water and heated to 80 ℃. The stirrer speed was then brought to 350rpm, and 40g of potassium phosphate, 140g of 1, 4-diiodooctafluorobutane, 14.6g of MV5CN, 330g of emulsifier and 20g of APS were then added. The reaction was rinsed into the reactor using 2500g of deionized water. The vacuum was broken with HFP. Immediately after this addition, the reactor was pressurized with an HFP/VDF ratio of 0.88 and a TFE/VDF ratio of 1.0 until the reactor reached a pressure of 1.5 MPa. Once this pressure was reached, the monomer ratio was changed to 1.24 for HFP/VDF and 0.73 for TFE/VDF. The reaction was run until 25% solids was reached, the reaction was stopped, and the latex was left in the reactor.
A block: the latex from the above B block still in the reactor was then brought to 60 ℃. Once at this temperature, 14.6g C6DV was added. While the reactor was at this temperature, the stirrer speed was set to 350rpm and the vacuum was broken with nitrogen. The reactor was brought to a pressure of 1.6MPa using an HFP/VDF ratio of 0.768 and a TFE/VDF ratio of 8.068. The reaction was run at the same rate until 30% solids was reached. The latex was then coagulated using a 1.25% magnesium chloride solution in deionized water and oven dried at 130 ℃ for 32 hours.
The fluorinated block copolymer has a Tg of-11 ℃ and a Tm of 250 ℃ as determined by DSC. The theoretical ratio of B blocks to A blocks is 80: 20.
Preparation example 5(PE-5)
B block (B): a40 liter reactor was charged with 22500g of deionized water and heated to 80 ℃. The stirrer speed was then brought to 350rpm, and 40g of potassium phosphate, 140g of 1, 4-diiodooctafluorobutane, 14.6g of MV5CN, 330g of emulsifier and 20g of APS were then added. The reaction was rinsed into the reactor using 2500g of deionized water. The vacuum was broken with HFP. Immediately after this addition, the reactor was pressurized with an HFP/VDF ratio of 0.88 and a TFE/VDF ratio of 1.0 until the reactor reached a pressure of 1.5 MPa. Once this pressure was reached, the monomer ratio was changed to 1.24 for HFP/VDF and 0.73 for TFE/VDF. The reaction was run until 25% solids was reached, stopped, and left in the reactor.
A block: the latex from the above B block still in the reactor was then brought to 60 ℃. Once at this temperature, 20g MV32I was added. While the reactor was at this temperature, the stirrer speed was set to 350rpm and the vacuum was broken with nitrogen. The reactor was brought to a pressure of 1.6MPa using an HFP/VDF ratio of 0.768 and a TFE/VDF ratio of 8.068. The reaction was run at the same rate until 30% solids was reached. The latex was then coagulated using a 1.25% magnesium chloride solution in deionized water and oven dried at 130 ℃ for 32 hours.
The fluorinated block copolymer has a Tg of-11 ℃ and a Tm of 258 ℃ as determined by DSC. The theoretical ratio of B blocks to A blocks is 80: 20.
Preparation example 6(PE-6)
B block (B): a40 liter reactor was charged with 22500g of deionized water and heated to 80 ℃. The stirrer speed was then brought to 350rpm, and then 40g of potassium phosphate, 140g of 1, 4-diiodooctafluorobutane, 330g of emulsifier and 20g of APS were added. The reaction was rinsed into the reactor using 2500g of deionized water. The vacuum was broken with HFP. Immediately after this addition, the reactor was pressurized with an HFP/VDF ratio of 0.88 and a TFE/VDF ratio of 1.0 until the reactor reached a pressure of 1.5 MPa. Once this pressure was reached, the monomer ratio was changed to 1.24 for HFP/VDF and 0.73 for TFE/VDF. The reaction was run until 25% solids was reached, the reaction was stopped, and the latex was left in the reactor.
A block: the latex from the above B block still in the reactor was then brought to 71.1 ℃. While the reactor was at this temperature, the stirrer speed was set to 350rpm and the vacuum was broken with nitrogen. The reactor was brought to a pressure of 1.6MPa using an HFP/VDF ratio of 0.768 and a TFE/VDF ratio of 8.068. The reaction was run at the same rate until 30% solids was reached. The latex was then coagulated using a 1.25% magnesium chloride solution in deionized water and oven dried at 130 ℃ for 32 hours.
The fluorinated block copolymer has a Tg of-11 ℃ and a Tm of 258 ℃ as determined by DSC. The theoretical ratio of B blocks to A blocks is 80: 20.
A summary of the Tg, Tm and modulus at 100 ℃ of the various polymers measured using the test methods described above is shown in table 1 below.
TABLE 1
Polymer and process for producing the same PE-1 PE-2 PE-3 PE-4 PE-5 PE-6
Tg(℃) -11 -11 -11 -11 -11 -11
Tm(℃) 266 249 254 250 258 258
Modulus at 100 ℃ (MPa) 1.88 0.51 0.76 0.48 0.63 0.72
Examples 1-5 and comparative example 1(EX-1 to EX-5 and CE-1)
Each of the above polymers was compounded separately in about 400g batches on a two-roll mill as follows: 100 parts of polymer, 30phr of carbon black, 3phr of auxiliary and 2phr of peroxide. The compounded polymers were tested for "cure rheology" and "physical properties" as described above, and the results are reported in table 2.
TABLE 2
Figure BDA0002134695010000321
Figure BDA0002134695010000331
Foreseeable modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention. The present invention should not be limited to the embodiments shown in this application for illustrative purposes. If there is any conflict or conflict between the present specification, as written, and the disclosure in any document incorporated by reference herein, the present specification, as written, will control.

Claims (15)

1. A curable composition comprising:
a fluorinated block copolymer having
(a) At least one A block, wherein the A block is a semi-crystalline segment comprising repeating divalent monomer units derived from at least one fluorinated monomer;
(b) at least one B block, wherein the B block is a segment comprising repeating divalent monomer units derived from a nitrile-containing cure site monomer and the following components:
(i) 45-85% by weight of vinylidene fluoride (VDF), 15-45% by weight of Hexafluoropropylene (HFP) and 0-30% by weight of Tetrafluoroethylene (TFE);
(ii)50-80 wt% VDF, 5-50 wt% fluorinated vinyl ether and 0-20 wt% TFE;
(iii)20-30 wt% VDF, 10-30 wt% non-fluorinated olefin, 18-27 wt% HFP and/or fluorinated vinyl ether, and 10-30 wt% TFE; or
(iv)25-65 wt% VDF, 15-60 wt% HFP and optionally at least 0.1 wt% and up to 30 wt% of other comonomers.
2. The curable composition of claim 1, wherein the nitrile-containing cure site monomer comprises at least one of: CF (compact flash)2＝CFO(CF2)5CN、CF2＝CFOCF2CF(CF3)OCF2CF2CN、CF2＝CFOCF2CF(CF3)OCF2CF(CF3)CN、CF2＝CFOCF2CF2CF2OCF(CF3) CN, and combinations thereof.
3. The curable composition of claim 1, wherein the a block is derived from TFE and less than 5 wt% comonomer.
4. The curable composition of claim 1, wherein the a block is derived from TFE, HFP, and VDF.
5. The curable composition of claim 1, wherein the fluorinated block copolymer has a melting point of at least 100 ℃ and at most 275 ℃.
6. The curable composition of claim 1, wherein the B block is semi-crystalline.
7. The curable composition of claim 1, wherein the B block is amorphous.
8. The curable composition of claim 1, wherein the Tg of the a block is greater than 0 ℃ and less than 80 ℃.
9. The curable composition of claim 1, wherein the Tg of the B block is less than 0 ℃.
10. The curable composition of claim 1, wherein at least one of the following is derived from a diolefin monomer: the A block, the B block, or both the A block and the B block, the diolefin monomer having the formula
Figure FDA0003482112130000021
Wherein R is1、R2、R3、R4、R5And R6Independently an H, C1-C5 alkyl group or a C1-C5 fluorinated alkyl group; and Z is a linear or branched alkylene or cycloalkylene group C1-C18 optionally containing oxygen atoms and optionally fluorinated.
11. The curable composition of claim 1, wherein the fluorinated block copolymer comprises from 0.05 wt% to 1 wt% iodine, based on the weight of the fluorinated block copolymer.
12. The curable composition of claim 1 further comprising a peroxide cure system.
13. The curable composition of claim 1, wherein the fluorinated block copolymer has a glass transition temperature of less than-20 ℃.
14. The curable composition of claim 1, wherein the fluorinated block copolymer has a modulus of at least 0.1MPa and at most 2.5MPa at 100 ℃ as measured at a strain of 1% and a frequency of 1 Hz.
15. A cured article derived from the curable composition of any one of the preceding claims.
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